Study On The Synthesis Of Three High Nitrogen Heterocyclic Energetic Compounds BNTF ANTF,and DANBT

High nitrogen energetic heterocyclic compounds have received a great deal of attention from researchers because of their high density, preferable molecular stabilities, low sensitivities and excellent detonation performances. The main content of this paper is the synthesis of 3,4-bis(4’-nitrofurazan-3’-yl)furazan(BNTF), 3-(4-aminofurazan-3-yl)-4-(-4-nitro furazan-3-yl)furazan(ANTF) and 1-amino-3-nitro-5-(5-amino-3-ntiro-1,2,4-triazole-1-yl)-1,2, 4-triazole(DANBT). Our analytic works in concrete are mainly as follows:(1) 3,4-bis(4’-nitrofurazan-3’-yl)furazan(BNTF) was synthesized by 50% H2O2/ vitriol /Na2WO4·2H2O to oxidize intermediate 3,4-bis(4’-aminefurazan-3’-yl)furazan(BATF), which was synthesized by reducing 3,4-bis(4’-aminefurazan-3’-yl)furoxan(BAFF) with Sn Cl2. Its structure was characterized by infrared spectrum(IR), mass spectrum(MS), nuclear magnetic resonance(NMR) and element analysis. The single crystal of BNTF was cultivated in ethanol and its crystal structure was determined by a fourcirde X-ray diffactometer. The results showed that the crystal was orthorhombic, space group P212121, a = 7.1261(10) ?, b = 9.7706(13) ?, c = 15.223(2) ?, Z=4, Dc=1.856 g/cm3. The thermal behavior of BNTF was studied preliminary by differential scanning calorimetry(DSC), the melting point was 84 °C. And an optimal process conditions were obtained: reaction temperature 35 °C, reaction time 2 h, ratio of n(BATF) : n(50% H2O2) : n(H2SO4) : n(Na2WO4·2H2O)=1: 50 : 40 : 1, and the yield of BNTF was 89.3%.(2) 3-(4- aminofurazan-3-yl)-4-(-4-nitrofurazan-3-yl)furazan(ANTF) was synthesized by 30% H2O2/ vitriol /Na2WO4·2H2O to oxidize 3,4-bis(4’-aminefurazan-3’-yl)furazan(BATF). Its structure was characterized by infrared spectrum(IR), mass spectrum(MS), nuclear magnetic resonance(NMR) and element analysis. The single crystal of ANTF was cultivated in acetonitrile and its crystal structure was determined by a fourcirde X-ray diffactometer. The results show that the crystal is monoclinic, space group P212121, a = 7.1261(10) ?, b = 9.7706(13) ?, c = 15.223(2) ?, Z= 4, Dc=1.856 g/cm3. The thermal behavior of ANTF was studied preliminary by differential scanning calorimetry(DSC), the melting point and composition peak are 101 °C and 298.6 °C, respectively. And an an optimal process conditions were obtained: reaction temperature 25 °C, reaction time 4 h, ratio of n(BATF) : n(30% H2O2) : n(H2SO4) : n(Na2WO4·2H2O)= 1: 16 : 16 : 1, and the yield of BNTF was 55.1%.(3) Given the hydrogen atom of 5-amino-3-nitro-1,2,4-triazole(ANTA) in 1 position could be replaced by nucleophilic, and the nitro group of 1-amino-3,5-dinitro-1,2,4-triazole(ADNT) in 5 position could be substituted by electrophilic reagents, so 1-amino-3-nitro-5-(5-amino-3-ntiro-1,2,4-triazole-1-yl)-1,2,4-triazole(DANBT) was synthesized by ADNT with ANTA in an alkaline solution. Its structure was characterrized by infrared spectrum(IR), mass spectrum(MS) and element analysis. The thermal behavior of ANTF was studied preliminary by DSC, the melting point and composition peak are 221.8 °C and 291.8 °C, respectively. And an optional reaction conditions were obtained: reaction temperature 56 °C, reaction time 4 h, ratio of n(ANTA): n(ADNT)=1.1:1, and the yield of DANBT was 50%.(4) Thermal decomposition and kinetics of ANTF were studied by using DSC under non-isothermal. The decomposition temperature of ANTF was 247.6 °C, and the apparent activation energy was 114.25 k J·mol-1. The impact sensitivity of BNTF was tested. The detonation performances of BNTF, ANTF, and DANBT were calculated by theoretical calculation of quantum chemistry.